T. W. MASTIN,GEORGE R. NORMAN AND E. A. WEILMUENSTER
I662
ICUNTRIBUTION
FROM THE CHEMICAL
RESEARCH LABORATORIES, THE LUBRI-ZOLCORP., CLEVELAND,
Vol. 67 OHIO]
Chemistry of the Aliphatic Esters of Thiophosphoric Acids. I BY T. W. MASTIN,GEORGE R. NORMAN AND E. A. WEILMTJENSTER sulfur atoms in this salt because of the fact that he could not obtain the intermediate diethyl chlorothionophosphate, VI. Pistschimuka states that this chloro compound probably does not exist, in spite of the fact that C a r i d claimed to have synthesized it. Carius, however, did not support his claim by published analyses and physical data. We have isolated the lead salt VIII from the reaction product of potassium hydrosulfide and VI. It was obtained as white needles, m. p. 74'. This synthesis leaves no doubt as to the position Discussion of the sulfur atoms in VIII. Compound VI11 was A brief outline of the reactions carried out in also isolated from the reaction product of phosthis investigation is shown in the diagram. Com- phorus pentasulfide and ethanol. A mixed meltpounds I' and V3 are reported in the literature. ing point of the salts obtained by the two methods Pistschimuka reported a salt similar to 11, pro- showed no depression. To further substantiate these results the acid duced by the hydrolysis of I . Salt formation was product obtained from the reaction of n-butanol indicated a t the oxygen atom. We obtained a potassium salt I1 by three differ- and phosphorus pentasulfide was converted to a ent methods, as indicated in the diagram. The mercuric salt IX. A mercuric salt was also product obtained by each method melted a t 197". prepared from the reaction product of potassium The mixed melting points showed no depression. hydrosulfide and VII. The salt obtained by Consequently I1 may be (a) potassium diethyl either method melted a t 61-62', A mixed meltthionophosphate, (b) potassium 0,O-diethylthiol- ing point showed no depression. As a consequence of this work we choose to phosphate or (c) the salt of a thiophosphate acid whose structure must be explained by resonance. write the reaction of aliphatic alcohols and phosIn the latter case only one potassium salt would phorus pentasulfide as follows exist. 4ROH f PIS5 --+Z(R011PSSH + H I S
For some time we have been interested in the chemistry of the esters of thiophosphoric acids. -4 review of the work that has been done in this field indicated the need for a systematic structural study. In 1912 P. S. Pistschimuka' published a paper in which he briefly reviewed the chemical literature previous to the beginning of our oivn work in this field. His three papers appearing in 1908, 19112 and 1912l constitute the outstanding contributions since the beginning of the century.
ROH
I
I"' -
( GHSO)ZPSOK
Pb(0Ac)z
"t 2
6011
IC?HrO)zPOCI \*
In addition to VI and VII, three other new chloro compounds were prepared: S,Sdiethyl chlorodithiophosphate, (CzH6S)2POCl(Xj; di[(czH~o)~PSS~~Pb ethyl chlorotrithiophosphate, VI11 (C2H&3)2PSCI (XI); and n[(n-C4HIO)2PSS]2Hg butyl dichlorothionophosIX phate, n-C4H$OPSCh (XII). Carius5 mentioned X and XI but again failed to characterize these compounds. The present report, therefore, constitutes the first characterization of VI, VII, X, X I and XI1 appearing in the chemical literature. Attempts to prepare salts from X and X I by use of potassium hydroxide or potassium hydrosulfide have been unsuccessful to date. Experimental Part A. Ethyl Compounds
(R0)zPSSK-1 111, R = CaH6 I V , K = n-C*Ho
HgCl
7
\ 7
(R0)zPSCl
VI, R = C2H5 1.11, R = n-CcHu
Pistschiiiiuka isolated a lead salt of a diethyl dithiophosphoric acid, produced from the reaction of phosphorus pentasulfide and ethanol, m. p. 74'. He was unable to determine the positions of the (1) P. S. r'istschimuka, J . Russ. Phys.-Chcm. Soc., 44, 1406-1554 (1912). (2) P. S. Pistschimuka, J . p m k f . Chem., 84, 746-760 (1911); Bcr., 41, 3854 (1908). (3) Wichelhaus, A n n . , Spl., 6, 263 (1870); J. Walczynska, Roczniki Chem., 8, 11&119 (1926). (4) The nomenclature rnrployed in this paper is proposed hy Dr. \ l i i r v hl:,
